On the reactivity of [IrCl(N2)(PPh3)2] with alkynylsilanes - A new route to vinylidene iridium(I) complexes |
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Authors: | Marcin Konkol |
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Affiliation: | Institut für Anorganische, Chemie der Martin-Luther-Universität Halle-Wittenberg, Fachbereich Chemie, Kurt-Mothes-Strasse, 2, D-06120 Halle (Saale), Germany |
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Abstract: | The iridium dinitrogen complex [IrCl(N2)(PPh3)2] (1) was found to react with alkynylsilanes to form the vinylidene iridium(I) complexes trans- (R/R′ = Ph/Me, 2; Me/Me, 3; Bn/Me, 4; SiMe3/Me, 5; SiEt3/Et, 6; iPr/Me, 7) and with Me3SiCCC(O)R to yield the iridium η2-alkyne complexes trans-[IrCl{η2-Me3SiCCC(O)R}(PPh3)2] (R = OEt, 9; Me, 11). Complex 9 was found to isomerize upon heating or upon UV irradiation yielding the vinylidene complex trans-[IrCl{CC(SiMe3)CO2Et}(PPh3)2] (10). The reaction of 1 with Me3SiCCCCSiMe3 yielded the complex trans-[IrCl{CC(SiMe3)CCSiMe3}(PPh3)2] (8), whereas with MeO2CCCCO2Me the iridacyclopentadiene complex [Ir{C4(CO2Me)4}Cl(PPh3)2] (13) was formed. The complexes were characterized by means of 1H, 13C and 31P NMR spectroscopy as well as by IR spectroscopy and microanalysis. |
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Keywords: | Iridium Alkynylsilane Vinylidene complexes η2-Alkyne complexes Iridacyclopentadiene |
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